Unexpected migration of the indenyl ligand in the reaction of alkynyl(η⁵-indenyl)iron complexes with phosphanes and phosphites from iron to the alkynyl group

Abstract

Novel indenylvinylidene iron complexes are formed in the reaction of alkynyl(η⁵-indenyl)iron complexes with phosphites and phosphanes in large excess by an intermolecular transfer of the indenyl ligand from iron to the C_β atom of the alkynyl ligand; mechanistic studies indicate that the reaction proceeds by a radical pathway.

References

1. See for example: J. A. S. Howell and P. M. Burkinshaw, Chem. Rev., 1983, 83, 557; F. Basolo, Inorg. Chim. Acta, 1985, 100, 33; J. M. O'Connor and C. P. Casey, Chem. Rev., 1987, 87, 307; F. Basolo, Polyhedron, 1990, 9, 1503.
2. A. J. Hart-Davis and R. J. Mawby, J. Chem. Soc. A, 1969, 2403.
3. See, for example: η⁵→η³: T. C. Forschner, A. R. Cutler and R. K. Kullnig, Organometallics, 1987, 6, 889 η⁵→η¹: H. Werner and A. Kühn, Angew. Chem., 1979, 91, 416; Angew. Chem., Int. Ed. Engl., 1979, 91, 447; C. P. Casey and W. D. Jones, J. Am. Chem. Soc., 1980, 102, 6154.
4. C. P. Casey, J. M. O'Connor and K. J. Haller, J. Am. Chem. Soc., 1985, 107, 1241.
5. C. A. Gamelas, E. Herdtweck, J. P. Lopes and C. C. Romãao, Organometallics, 1999, 18, 506.
6. See, for example: W. G. Bentrude, Phosphorus Sulfur, 1977, 3, 109; B. P. Roberts, Adv. Free Radical Chem., 1980, 6, 225.
7. H. Kandler, C. Gauss, W. Bidell, S. Rosenberger, T. Bürgi, I. L. Eremenko, D. Veghini, O. Orama, P. Burger and H. Berke, Chem. Eur. J., 1995, 1, 541.
8. C. Bianchini, F. Laschi, D. Masi, F. M. Ottaviani, A. Pastor, M. Peruzzini, P. Zanello and F. Zanobini, J. Am. Chem. Soc., 1993, 115, 2723.